This invention relates generally to optical emitters and, in particular, to the use of semiconductor quantum dots, nanocrystals and particles as fluorescent coding elements.
Semiconductor quantum dots are simple inorganic solids typically consisting of a hundred to a hundred thousand atoms. They emit spectrally resolvable energies, have a narrow symmetric emission spectrum, and are excitable at a single wavelength. Semiconductor quantum dots have higher electron affinities than organic polymers, such as those used as hole conductors in current display technology. They offer a distinct advantage over conventional dye molecules in that they are capable of emitting multiple colors of light. In addition, semiconductor quantum dots are size tunable, and when used as luminescent centers for electron hole recombination for electroluminescent illumination, their emission color is also size tunable. Another advantage is that the quantum dots are photochemically stable under UV excitation. Reference in this regard may be had to an article entitled: xe2x80x9cSemiconductor Nanocrystals as Fluorescent Biological Labelsxe2x80x9d (M.Bruchez Jr. et al, Science (281), 1998).
Because semiconductor quantum dots emit a narrow linewidth, are efficient emitters, and are tunable by their quantum size effect, they are suitable for coding, labeling and authentication, applications. Another advantage associated with semiconductor quantum dots, also referred to nanocrystals, is that they may be universally excited utilizing one UV source and therefore there is no need for multiple sources.
However, further investigation of the physical properties and interactions of quantum dots reveal some impediments to their use in practical applications.
One of the phenomena that quantum dots exhibit is chromophore tuning related to their quantum size, known as the xe2x80x9cQuantum Size Effectxe2x80x9d. Dyes utilizing nanocrystals are exemplary systems for testing the xe2x80x9cparticle in 1-D boxxe2x80x9d model of quantum mechanics as shown in FIG. 1. This is because, among other things, they exhibit absorption and emission characteristics and may be optically directed with nonlinear optics (e.g. X(3)).
Reference in this regard may be had to Kuhn, H.: Progress in the Chemistry of Organic Natural Products, ed. by D. L .Zechmeister, Vol. 16 (Springer, Wien 1959) p.17, and also to Fxc3x6rsterling, H. D., H. Kuhn: Physikalische Chemie in Experimenten. Ein Praktikum (Verlag Chemie, Weinheim/Bergstr.1971) p.373.
As an example, thiacyanine dyes (MWxcx9c600 a.m.u.) with a quantum dot size (a) of approximately 1.5 nm, and an emission wavelength (xcex) of 500 nm, exhibit the characteristics shown in equations 1 and 2 of FIG. 2.
However, there are limits to the tunability that may be achieved by the quantum size effect. It is well known that the energy gap and excitation emission can be tuned by size according to equation 3 shown in FIG. 2. However, electrons and holes have xe2x80x9ccollisionsxe2x80x9d with the walls and broaden the excitation line ("ugr") according to equation 4, where VF is a Fermi velocity xcx9c105m/sec.
For example, using the quantum dot size of a=4 nm, the change in the excitation line (xcex94"ugr"v) would be 2.5xc3x971013 with a corresponding wavelength spread (xcex94xcex) of 30 nm at 600 nm. A quantum dot size of 2 nm exhibits a wavelength spread (xcex94xcex) of 60 nm at 600 nm.
In general, quantum dots smaller than 2 nm will have emission lines broader than dyes, as shown in FIG. 3.
As the quantum size shifts, the ratio of the shift in size and the resulting change in line width is shown in equation 5 of FIG. 2. When the shift to width ratio becomes unity, tuning is no longer effective for coding. The quantum size resulting in a shift to width ratio of 1 is 4 nm, as determined by equation 6 of FIG. 2. Thus, quantum dots larger than 4 nm will have shifts less then the emission linewidth.
In summary of the analysis of the characteristics of semiconductor quantum dots thus far, when coding and labeling with semiconductor nanocrystals or quantum dots, the following considerations should be taken into account:
1) The room temperature linewidth is approximately 30 nm (2.5xc3x971013 secxe2x88x921) as opposed to dyes which typically have 40-60 nm linewidths.
2) Separate peaks require 2"sgr" separation of approximately 60 nm as opposed to dyes with 90 nm separation requirements.
3) A code density of 2Mxe2x88x921 may be achieved where M is the number of resolvable quantum dot emission peaks.
Combinatorial coding with quantum dots also presents complications related to trap states. Quantum dots have broad secondary peaks joining the excitonic emission as shown in FIG. 4. At 30% quantum efficiency, this broad peak has an amplitude half as high as the narrow 20 nm wide emission. As a result, the overlapping broad peaks restrict combinatorial coding with quantum dots even more than dyes.
Another factor to be considered when utilizing semiconductor quantum dots for coding and labeling applications is that the quantum efficiency of a quantum dot is affected by the interaction of carriers with the surfaces of the quantum dot. Surface atoms are not a bulk phase and are not generally amenable to lattice matched passivation (e.g., ZnS shell).
Reference in this regard may be had to xe2x80x9cQuantum Dot Bioconjugates for Ultrasensitive Nonisotopic Detectionxe2x80x9d, by Chan, W. C., Nie, S., Science, 281(5385):2016.
The ratio of surface atoms to bulk in a quantum dot is shown by equation 7 of FIG. 5, where d is a lattice constant. For a quantum size of 3 nm and a lattice constant of 0.3 nm, the ratio Ns/Nb from equation 7 is approximately 30-40%, and therefore the quantum efficiency is approximately equal to R. Thus, the smaller the quantum dot, the lower the quantum efficiency, which further limits size tuning.
Semiconductor nanocrystals and quantum dots typically have quantum efficiencies of 5%-25% after some form of passivation. They are primarily comprised of surface or interface atoms which trap photo-carriers in picoseconds and relax with microsecond decays. This slow decay makes even their pulsed (flash lamp) excitation saturate at Is=10 KW/cm2. This is in contrast to dye chromophores which have 30%-95% quantum efficiencies, for example, Isxcx9cMW/cm2, and may in some instances produce amplification.
A comparison of the light output of quantum dots and dye chromophores may be made using the following relationships shown in FIG. 5. The fluorescent output is shown by equation 8, the saturation intensity (Is) is shown by equation 9, and the maximum output (Ioxcx9cIs) is derived from equation 10. The ratio of light output from a dye and quantum dots (Dye/QD) is approximately 3xc3x97103 as shown by equation 11.
It has been stated in prior art publications that the fluorescence intensity of a single quantum dot is equivalent to that of approximately 20 rhodamine molecules. However, when compared on an equivalent molecular weight basis, the results are quite different. For example, a comparison of a quantum dot structure with a CdSe core (excluding the ZnS shell) having a mass of approximately 100,000 a.m.u. with a Rhodamine6G (R6G) molecule having a mass of approximately 500 a.m.u., shows a relative intensity ratio (IR6G/IQD)of 10 when compared on an equivalent molecular weight basis.
While quantum dots are known to be photochemically stable under UV excitation, the utilization of UV sources involves some disadvantages including UV decomposition of synthesis products, singlet O2 generation and reactions, and energetic recombination, trapping and photodegradation of the nanocrystals.
Another aspect of the photo-stability of semiconductor quantum dots to be considered is photo-darkening. Occurrences of photo-darkening are known in the applications utilizing semiconductor quantum dots, particularly with glass-based and polymer passivation. This is further complicated by the fact that the degree of passivation may not be universal or consistent and thus may vary with each semiconductor. This is disadvantageous when using semiconductor nanocrystals as optical or e-beam phosphors.
It has also been stated in the prior art that the quantum dot emission (time constant txc2xd=960 s) is nearly 100 times as stable as rhodamine 6G(R6G) (txc2xd=10 s) against photobleaching. However, on an equivalent mass basis, after approximately 1 minute of exposure, the intensity of R6G (IR6G) is approximately the same as the intensity of the quantum dot structure (IQD) In addition, dyes often recover from photobleaching while quantum dots typically do not.
It can be seen then that size tuning of quantum dots may yield less than optimum results, in particular when utilizing semiconductor quantum dots for fluorescence labeling and coding applications. As mentioned above, some disadvantages associated with practical applications include the fact that smaller dots (xe2x89xa62 nm) create wider emissions and even lower quantum efficiencies, while sizes larger than 4 nm produce shifts smaller than a linewidth. In addition, quantum dots are difficult to passivate on a consistent basis and exhibit broad spectrum ( less than 100 nm) trap emission and photobleaching. As was shown above, on a volume or mass basis, quantum dots are less optically efficient than dyes, and quantum dots offer significantly less coding capacity than dyes per unit wavelength.
The foregoing and other problems are overcome by methods and apparatus in accordance with embodiments of this invention.
A method is disclosed for obtaining information about an object, as is a system operating in accordance with the method. The method includes steps of (a) placing a plurality of regions onto the object, each region being capable of emitting a predetermined wavelength of light; (b) detecting the light; and (c) decoding information from the detected light. At least one of the regions contains semiconductor particles having a radius larger than a quantum dot radius for a corresponding semiconductor material, and a chemical composition selected to provide the predetermined wavelength of light. The semiconductor material contains at least one of a Group II-VI alloy, or a Group III-V alloy, or a compound comprised of an indirect bandgap material, such as Si or Ge. The concentrations of the alloy or compound constituent elements are preselected to provide the predetermined emission wavelength. The semiconductor material may further include a selected dopant.
In some embodiments (e.g., some Group II-VI and Group III-V embodiments) the semiconductor material alloy has the form ABxC1xe2x88x92x, where A, B and C are each a different element, and in this case in at least two of the plurality of regions the value of x can be made different.